TWI362304B - Method for consolidating tough coated hard powders - Google Patents

Description

1362304 IX. Description of the Invention: [Technical Field of the Invention] The present invention discloses a method of consolidating a tough, coated hard powder (TCHp) to a substantially complete density at low or no pressure and an article consolidated by the method. This method is a cost effective method for producing sintered bodies of TCHp materials based on liquid phase sintering, which provides an added value over conventional hard objects and materials known in the art. [Prior Art] φ can be defined as a powder or compact heat treatment for the purpose of causing the particles to join to produce a solid object. In certain applications where the powder consists of a powder mixture of at least two different materials having different melting points, the powder mixture is pressed into a porous ("raw") body 2 to heat the body above the lowest melt composition. The spots are condensed and a portion of the compacted loose powder mixture is liquefied. After the sintering temperature is maintained for a predetermined period of time, the material is allowed to cool, the liquid solidifies, and the body is "bonded" into a densified useful structure. Examples of such systems are copper/tin, iron/copper, and carbonized cranes/ • Ming. In these methods, the compaction of the compacted body is carried out in the presence of a liquid phase, and such sintering methods are referred to as "liquid phase sintering" (Lps) ^ in some systems, in particular, hard metals &quot (eg, tungsten carbide) and other ceramic particles (LPS) are sometimes referred to as conventional sintering. In the Lps method, it is advantageous to have a certain minimum amount of liquid present at the sintering temperature to ensure the transport of the binder phase, " to achieve uniform distribution and densification. In order to avoid zero-piece deformation and grain growth, it is also advantageous to limit the amount of liquid phase present. 102496.doc For example, the liquefaction enables increased material transport, particle rearrangement, growth skeletal structure, and compactness. It is generally believed that this is achieved by rounding the particles as the external irregularities liquefy and the liquid migrates to fill the voids. Upon cooling, recrystallization occurs and grain growth often occurs. Porosity (as a percentage of the total volume) may be reduced due to structural compaction. For example, the compaction rate may be affected by, for example, sintering temperature, sintering time, sintering pressure, sintering gas, and the weight fraction of the cement component present. Liquid phase sintering of conventional hard metals such as tungsten carbide-cobalt (wc_co) compacts is generally carried out at a sintering temperature in the range of from 1325 °C to 1475 °C. Since the Wc_c compact is heated during the WC-Co hard metal sintering, the cobalt begins to have very viscous liquid properties at about 700 ° C, and the diffusion increases with increasing temperature as the viscosity decreases accordingly. Since c〇 tends to be as wet as possible on the surface of wc, the oily nature and viscosity of the salty Co metal produce capillary appeal. This causes the WC particles to rearrange and the composite begins to shrink, even before the first liquid phase is formed. At 1275 °C, the Co bond metal begins to dissolve the wc particles, and the ternary eutectic reaction begins to form the Co-W-C alloy. As the temperature continues to increase, the increased surface wetting, liquefaction, and capillary forces cause the particles to continue to rearrange, and as the grain boundaries move through the interface between the WC grains and the c〇 bond phase, the powder mass shrinks into the shape of the desired article. The high density, uniformity and wc stoichiometry of sintered parts are the basic needs of wc_c〇 microstructural integrity and strength, ensuring proper local carbon balance during liquid phase sintering to eliminate the formation of CwWsC 7 phase of brittle carbon and caused by too much carbon The carbon porosity, which provides a fracture toughness for WC-Co materials, is also heavy I02496, doc 1362304. The porosity at which the deprivation strength is removed and the grain growth in the microstructure can be achieved by selecting a suitable sintering temperature and pressure. For example, the temperature must be high enough to liquefy the foot material to achieve the transfer of material necessary to fill the pores between the particles while maintaining a sufficiently low temperature to avoid trade leading to grain growth (: over/combination. insufficient capillary force) An external pressure can be applied to provide a densification to a range close to the theoretical density. In conventional sintering, a small percentage (3 to 18% by weight) of cobalt is generally mixed with the cobalt. The cobalt binder plays a certain role in densification, and is in wc_c〇 Uniformity is achieved in the microstructure, which requires uniform distribution. Microstructural defects are generally found in sintered WC-Co parts. The general reason is that the WC and Co powders of approximately equal diameter are incompletely blended (even for a long time)^ Therefore, this method is required to encapsulate (or at least partially bind) each of the ruthenium particles in just the right amount c〇 so that the ratio of Co to WC is substantially uniform throughout the mixture. It is highly unlikely that this result is statistically obtained because cobalt is not sufficient. Small nanoparticles are obtained so that they cannot be uniformly blended with WC particles. Cobalt oxidation, explosive spontaneous combustion reaction and particle agglomeration are obstacles to their availability. The result is a WC_C〇 mixture with cobalt-rich and cobalt-depleted regions. The liquid phase first appears in the Co-rich region, while the WC-unsaturated cobalt seeks a thermodynamic equilibrium by: (a) consuming nearby smaller WC crystals ( The smallest may be consumed entirely) and (b) the unsaturated c〇 moves over a long distance to the lean c〇 region to dissolve more and more WC' until saturation is achieved. Therefore, it is necessary to balance and adequately Co liquid to wet the WC particles. At the same time, it is required to liquefy and transport cobalt to the Co-poor region at a higher temperature than that required to produce the liquid phase. The effect of the uneven Co distribution is generally utilized (a) when a very long ball mill is used, 102496.doc 1362304, (b) High sintering temperature, and (4) longer sintering time. Ball milling tends to reduce many WC particles into fine powder, which is preferentially dissolved by c〇 during heating. The latter two measures do help spread the cement phase and are sintered. During the period, the liquid cobalt distribution is normalized, but it is also dissolved by wc. In addition, some penetrate the wc particles along its grain boundaries because the wc/wc interface energy is higher (more active) than the WC/CO interface, at least at the grain boundaries. Pick up When present at the interface perpendicular to the surface. When cooled, the saturated arm.. Solution precipitates WC. When curing, preferential trade (: nucleation and recrystallization on adjacent remaining large undissolved WC crystals, resulting in no The ideal Ostwald ripening (grain growth) phenomenon. The grain growth continues until the temperature drops below the 1275X: ternary eutectic of the Co-WC system. The plot shows a pseudo binary WC- Co phase diagram. Nearly 100% of the sintered density is common for wc_c〇 materials. Increasing the sintering temperature therefore contributes to the fluidity of the binder, but also causes excessive WC dissolution to produce undesirable grain growth. There is a compromise between the sintering time and the need to pay attention to balance. The maximum temperature should be high enough to liquefy enough material 'to achieve the material transfer required to fill the pores between the particles (damage to structural strength), while trying to avoid too high temperatures for too long 'to avoid grain growth (grain growth) Reduce structural strength). Alternative sintering techniques have been utilized since controlling the sintering temperature to be a major aspect of high quality hard metal microstructures. These techniques include studying the reduction of sintering time (eg, microwave sintering) and the use of gas pressure (eg, hot pressing, hot pressing [HiP], and Ceracon and Roc-Tec sintering). - Forging method) to achieve consolidation at a lower temperature. 102496.doc 1362304 Another method of consolidating conventional hard metals is to increase the weight fraction of the cement (eg, Ming). This can be in the range of % by weight. This not only increases the amount of liquid, but can also have the beneficial effect of increasing the structural mobility... This method has two distinct drawbacks and is therefore generally avoided. First, increasing the weight percent of the cement reduces the weight percent of the wc (wear phase) in the structure and correspondingly reduces wear resistance. Secondly, it is known to increase the amount of slag and dissolve more wc, which significantly promotes grain growth during cooling. The only method used to improve the wear resistance of conventional carbides (while maintaining the high fracture rupture of WC-Co substrates) has been (4) continuous improvement and improvement of conventional powders and consolidation treatments. a thin abrasion resistant coating, and (4) laminating the quarter hard material to the WC_c crucible substrate. The modified wc_c〇 microstructure is a fine balance of time, temperature, grain size, and other product and process parameters. Through the better sintering temperature control and the use of higher purity, high homogeneity WC and Co starting powders, the gradual improvement of conventional carbides has been achieved in the past 50 years due to the introduction of external coatings for more than ten years. The improvement in the wear resistance of the material has slowed down almost to a standstill. Although such techniques have reduced the problems that occur in conventional hard metal liquid phase sintering, there is still a need for methods of fabricating particles having uniform properties of (4) and throughout the sintering process and the particles formed therefrom. . In order to avoid the aforementioned drawbacks, the present invention provides a method for solidifying particulate materials by liquid phase sintering - a new type of "designed microstructured particulate material", which is called a tough coated hard powder (TCHPS or EternAloy). The novel sintered particulate material family consists of one or more superhard Gadec c (Geidrat 102496.doc 1362304 Ο or larger ceramic or refractory alloy core particles) having extremely high wear resistance, lubricity and other properties. The particles (1) are each coated with a metal layer having a relatively high fracture toughness, such as WC or Tac, and (7) is also coated with a second layer containing a metal binder such as c〇 or Ni. The combination of multi-attribute alloys within the TCHP sintered structure allows the extreme properties of orthodontics (including, but not limited to, brilliance, abrasion, chemical resistance, and light weight) to be combined at various levels to provide a material that is not available with sintered homogeneous powder. The TCHP material is disclosed in U.S. Patent No. 6,372,346, the disclosure of which is incorporated herein in Learn the phase and extreme properties of incompatible materials. Therefore, TCHp materials can be designed so that the hardness close to diamond is greater than the fracture toughness of tungsten carbide and the weight of titanium. Therefore, the coffee can significantly exceed the conventional metal (4) And forming tools "abrasives, friction and wear products and thermal coatings, and abrasion resistance of automotive, aerospace, heavy industry, and anti-purple parts. [Invention] The present invention provides a method of forming an article from a particulate material. The invention comprises providing a plurality of core particles consisting of a core particle material or a plurality of different core particle materials selected from the group consisting of metal and metalloid nitrides, metal and metalloid carbides, metals and metalloids. Carbonitrides, metal and metalloid borides, metal and metalloid oxides, metal and metalloid sulfides, metal and metalloid tellurides and diamond. Provide an intermediate layer on most core particles. The intermediate layer consists of a second compound having a different core particle material and having a relatively high degree of fracture. No. 102496.doc 1362304 The core particulate material is bonded and capable of bonding with a metal layer selected from the group consisting of iron, cobalt, nickel, copper, titanium, aluminum, magnesium, lithium, lanthanum, silver, gold, platinum, and mixtures thereof to form coated particles. The outer layer is applied to the coated particles. The outer layer comprises a metal selected from the group consisting of iron, cobalt, nickel, and mixtures thereof, and a substantially continuous outer layer is formed on the intermediate layer. The coated particles and the outer layer combine to form component particles. The component particles form the article. The article is sintered to a substantially full density at a temperature sufficient to liquefy at least a portion of the outer layer without significant external consolidation pressure and sufficient to dissolve a portion of the intermediate layer in the liquid formed from the outer layer. The liquid formed by the layer solidifies before the liquid and the core particles are significantly detrimental. In a specific embodiment, the core particulate material has the chemical formula MaXb, wherein the germanium is selected from the group consisting of titanium, tantalum, niobium, vanadium, niobium, niobium, chrome, molybdenum, a metal of tungsten, aluminum, magnesium, copper, and bismuth; X is an element selected from the group consisting of nitrogen, carbon, boron, sulfur, and oxygen; and a and b are greater than 〇 and include 14. In another specific embodiment, the core particulate material is selected from the group consisting of TiN, τ丨CN,

TiC, TiB2, ZrC, ZrN, ZrB2, Hfc, HfN, HfB2, TaB2, VC, VN, eBN, hBN, Al2〇3, Si3N4, Xian6, siA1CB, b4c, b2o3, w2b5, Wb2, WS2, A1N, read Continent 4, m〇S2, MoSi, M02B5 and M0B2 o The metalloid elements are the elements along the line between the periodic table metal and the non-metal. Quasi-metals include sheds, stone eves, dragonflies, dragonflies, dragonflies and hooves. Needles are also often recognized as quasi-metals. Non-limiting examples of metalloid nitrides are cubic nitridation 102496.doc 1362304 boron (cBN) and in 3 teams. An example of a metalloid carbide is B4 (an example of a binary metalloid compound is SiB6. The invention also discloses a method of forming an article from a particulate material, comprising providing a plurality of core particulate materials or a plurality of different core particulate materials The core particles, such as selected from the group consisting of TiN, TiCN, D (1),

ZrC, ZrN, ZrB2, Hfc, fine, loud, Tam, _, _, Al2〇3, Si3N4, SiB6, SiAICB, ¥, ho], w2b5, WS2, interesting, AIMgBu, M〇S2, μ〇^, Mo2B5, MoB2, and diamonds; and f most of these core material materials provide an intermediate layer in an amount of from 1 〇 to 8 〇 by weight based on the weight of the article. Between the two, it generally consists of a composition different from the core particle material and has a relative A second compound having a higher breaking bristles, wherein the second compound is selected from the group consisting of wc, Tac, W2C, and a mixture of WC and W2C, thereby forming coated particles. The coated particles are generally treated as previously described, comprising applying an outer layer to the coated particles, the outer layer comprising a metal selected from the group consisting of iron, indium, nickel, and mixtures thereof to form a substantially continuous outer layer on the intermediate layer, thereby forming a component Particles; forming a plurality of component particles into an article; at a U force without significant external solids Μ A π 'sufficient to liquefy at least a portion of the outer layer Ό U dissolves between 5 and 90% by volume in the liquid formed from the outer layer The layer is sintered at a time to provide an effective amount of liquid to achieve a full density, the solid portion of the intermediate layer and the m layer inhibiting the interaction of the liquid with the core particles; and The liquid formed by the u τ gate layer cures before the liquid and the core particles are significantly detrimental to 102496.doc 1362304. Burning, calorific and time should be such that they do not cause complete interlayer dissolution, but some intermediate layers are partially dissolved, such as 5-50% intermediate layer dissolution or 50-99% intermediate layer 'combination'. Actually, intermediate layer The solid portion inhibits the chemical interaction of the liquid with the core particles. [Embodiment] This disclosure does not describe a method of encapsulating and burning, =/, fine particles having a desired group property with a grain boundary modifier having other properties, thus allowing design of a combination of material properties of the previous non-month b. TCHP"Building Blocks" granules contain multiple elements such as hardness + wear resistance + toughness + metal cement + other designer properties, and are optimized for simultaneous optimization at nano, micro, macro and functional levels. Quality materials engineer thousands of new grade materials. The combination of nanoencapsulation and particle sintering produces a pseudo-alloy structure that combines the residual phase and properties of the thermodynamically incompatible material. This combination allows these phases and properties to operate as complex components on the working surface and tool edges and as a heat application coating. Multiple combinations of properties such as low weight 4, low coefficient of friction, high/low thermal conductivity, lubricity and lubrication can be achieved without the traditional limitations imposed by alloying, lamination, mechanical properties and heat treatment. The methods described herein include forming an article from a particulate material. For example, particulate material or TCHPs include a plurality of & materials, an intermediate coating on most materials, and an overcoat on the particles. f In its powdered embodiment, the core particles may be a unique composite particulate material composed of a core particle or a plurality of different core particles selected from metal or metalloid nitrides and carbides. , carbon nitrogen:: 102496.doc •13. 1362304 shed compounds, oxides, sulfides and tellurides or diamonds. The core particle material is often a metal compound having the chemical formula MaXb, wherein the cerium is at least one element selected from the group consisting of titanium, lanthanum, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, aluminum, magnesium, steel, boron, and lanthanum. X is at least one element selected from the group consisting of nitrogen, carbon, boron, sulfur, antimony and oxygen. The letters & and 5 in the formula MaXb are greater than 0 to 14. Non-limiting examples of such compounds include TiN, TiCN, TiC, ZrC, ZrN, VC, VN,

Al2〇3, Si3N4, SiB6, SiAlCB 'W2B5, AIN, AlMgB丨4,

MoS2, MoSi2, m〇2B5 and Mo2B. In another embodiment, the plurality of core particles comprise at least one particle selected from the group consisting of diamond, cubic boron nitride, and hexagonal boron nitride, and mixtures thereof with each other or with any of the foregoing materials. In this article, •• is selected from "(ch〇sen fr〇m) or "from" (selected as the choice of the early component or two (or more) components. For example, X can Include only one of chaos, rabbit, collar, sulfur, sand, and oxygen, or may include any or all of these components. In other embodiments, most of the particles include WC, /, steel: 3⁄4 leather And to the intermediate layer of S Zene steel alloy, nitride 7 or carbonization group. These materials have a fracture degree greater than cubic nitride butterfly. However, it should be understood that the intermediate layer material only needs materials than the core particle. Has a relatively good fracture toughness' and can be bonded to a metal compound or material forming the core particles, and can also be selected from the group consisting of iron, cobalt, copper, titanium, samarium, magnesium, lithium, strontium, silver, gold and platinum. Metal Bonding. / In a non-limiting embodiment, the "coated particles have an average particle size of less than about a minor micron. In another embodiment, the coated particles 102496.doc • 14-1362304 may have less than loo micron. The average particle size is more than half, and it is recognized ~ for example, less than about 50 micro

-I coated (iv) less than about 1 micron. In another embodiment, the coated crucible has an average particle size in the "" to the surface nanometer range. In another non-limiting embodiment, the intermediate w-ancient-c 1 layer may have a thickness in the range of the core particles up to the crucible after sintering. The thickness of the intermediate layer has an effect on the mechanical properties of the article from which it is made. " Tian a in the specific example t, by the path method in the cross-sectional photomicrograph, when the coated particles (with the core of the intermediate layer) have an average particle directness of less than about 2 microns' The misalignment mobility in adjacent sintered particles is increased, which improves the mechanical properties of the sintered article. Even with the classical mechanical method, it is clear that the thickness of the spherical shell WC around the m-ball increases from about 0 m to about 4 m to increase the theoretical toughness. the above. In the wc, TaC, W2C or WC#D W2C coating reduction = about, the imaginary stress (image s (10) s) began to gradually increase the fracture enthalpy to be completely higher than predicted by finite element analysis. For example, "Louat", Journal of Metallurgy (Acta MetaUurgica), No. 33, No. 1, pp. 56-69 (1985) discusses that "imaginary stress" is defined as the inherent slip of microstructural dislocations. Newton resistance. The intermediate layers may be deposited by at least one selected from the group consisting of chemical vapor deposition, physical vapor deposition, plasma deposition, laser cladding, or deposition methods, plasma cladding, magnetic plasma deposition, and electrochemistry. Plating, electroless plating, sputtering, solid phase synthesis, solution chemical deposition methods, and combinations of these methods. Relying on one or more compounds being deposited, various precursors used in the deposited compound 102496.doc -15-1362304, layer deposition methods used in previous paragraphs, core particle chemistry, interlayer thickness, and desired coating properties In some embodiments, the intermediate layer is deposited at a temperature which can be at 2 Torr. 〇 to about 8000. Within the range of ’ 'for example, 20 ° C to 125 ° C. In other embodiments, the intermediate layer is deposited at a temperature, which may be at 125. 〇 to 18 〇 (rc, 1800 ° C to about 8000 X: and 200 to 80 (in the range of TC. Further) In some embodiments, the intermediate layer includes the weight of the article

A material selected from the group consisting of wc, TaC, W2C or WC and W2C in an amount ranging from 60% by weight to 98% by weight. In another embodiment, the intermediate layer comprises wc, TaC, WK or WC sum in an amount ranging from 10% to 60% by weight, based on the weight of the article. In another embodiment, the intermediate layer comprises wc in an amount ranging from 5 wt% to 1 wt%, based on the weight of the article,

TaC, W2C or WC and W2C. In some specific embodiments, the majority of the coated TCHP particles are then encapsulated by a layer of external cement that can be continuous. The layer may include ruthenium, ruthenium, iron, a mixture thereof, an alloy thereof, or an intermetallic compound thereof deposited on the outer surface of the second metal compound layer. The outer layer typically has a coated particle size of 3 after sintering. /. As for 2. /. The thickness of the range. The outer layer may further comprise at least one layer selected from the group consisting of other metals or ceramics, cements, sintering aids, and polymeric materials. The outer layer can be deposited by at least one of the following methods: chemical vapor deposition, physical vapor deposition, plasma deposition, laser cladding or deposition methods, plasma fusion-cladding, magnetic electropolymerization, deposition, electrochemical plating, electroless plating. Coating, sputtering, solid phase « δ or ' combined liquefaction dry deposition method and combinations thereof. In a specific embodiment of TCHP, the aforementioned outer layer comprises at least one compound selected from the group consisting of metals, ceramics, cements, sintering aids, waxes or polymeric materials. In the case of a bonding agent, a sintering aid, a crucible or a polymeric material, the coating may be completed by mixing or blending with or without heating in the range of 50 to 15 °C. The TCHP coating can be deposited over a wide temperature range using a number of different methods. CVD is the most common. The most common temperature range for CVD coating deposition is from 200 ° C to 80 Torr. Hey. However, higher temperatures (18 〇〇. 〇 to about 800 (TC) are typical for many methods such as plasma deposition, magnetic plasma deposition, pulsed laser deposition, and arc discharge. In addition, lower temperatures (20 ° C to 2001) Typical methods for chemical, electrochemical and electroless deposition of sol-gel baths. Like the intermediate layer, depending on the one or more compounds being deposited, the various precursors used for the deposited compounds, used in previous paragraphs Layer deposition method, core particle chemistry, interlayer thickness, and desired coating properties, each of the outer layer embodiments is deposited at different temperatures, and the outer layer can be deposited at temperatures ranging from 2 ° C to 650 ° C. In a specific embodiment The outer layer is deposited at a temperature ranging from 2 Torr to 12 5 ° C. In another embodiment, the outer layer is deposited at a temperature in the range of 125 to 65 ° C. In another embodiment, the outer layer may be Deposition at temperatures ranging from 200 ° C to 550 ° C. As mentioned previously, the outer layer of particles generally has a thickness in the range of 3% to 12% of the diameter of the coated particles after sintering. The thickness of the outer layer allows for a coated particle. Related to dislocation The strain field is transferred to the indirectly adjacent intermediate layer by the outer cement layer. In a specific embodiment, the outer layer comprises an amount of up to 45 wt.%, such as from about 0.5 wt% to 3.0 wt%, based on the weight of the article. In the embodiment 102496.doc, the outer layer comprises an amount in the range of more than 3.0% by weight to 18% by weight based on the weight of the article, and in another embodiment, the outer layer comprises in the range of more than 18% by weight to 45% by weight based on the weight of the article. The combination of the core particles 'intermediate layer and outer layer can form coated particles having an average particle size of less than about 1 micron. With the above powder, the sintered TCHP embodiment can be designed to be simultaneously present by the particle intermediate coating and the bonding agent. The common adjacent microstructure of the high fracture toughness of the layer composition 'sintered TCHP specific embodiment comprises a plurality of sintered TCHP coated composite particle edges having the above plurality of core particle compounds or elements. More than 30 different cores These combinations and arrangements of particulate compounds and elements give the TCHP family a unique combination of properties with unique properties. Typically, TCHPs are manufactured. Finally consolidating or cladding onto the object. Designing the consolidated TCHP article for a number of applications, such as applications requiring extreme wear resistance and toughness. In its consolidation embodiment, TCHps is Basically composed of a plurality of composite 7〇:111)3 coated particles sintered in a uniform whole, TCHP coated

A unique material type. In some embodiments, the particles are sintered in a liquid phase to form an article. In a specific embodiment, the liquid phase is sintered as a bonding agent. Consolidation in other specific ones can occur primarily from capillary forces.

I02496.doc •18· The entire unsintered compacted powder body is evenly distributed. In some embodiments, this can be achieved by adding a cobalt atom (or other material containing an outer layer on the particle) during coating to the target c〇:Wc ratio encapsulating the high adjacent WC coated TCHP particle. The surface is reached. This continues until the desired c〇:wc ratio is evenly distributed over the TCHP particles and the entire powder. This TCHp feature allows for multiple conditions to be adapted to different target TCHP compositions, for example, by (a) protecting the core particles from dissolution by the bonding agent, and (b) providing adjacent tough support structures. The result is a higher sintering temperature than those used in conventional WC-Co materials, while reducing the need for high external pressure without the risk of WC grain growth and strength loss. A more uniform Co-knife also produces better microstructure consistency and uniform distribution of anti-wear core particles. The resulting TCHP uniform microstructure has excellent microstructural integrity. This produces fewer structural defects and is further converted to better, more consistent material properties with attendant performance improvements. In certain embodiments, the sintering can be carried out under a variety of conditions for a sufficient time 'such as temperature and/or consolidation pressure to achieve a high in the outer layer, the intermediate layer, or both, in terms of the layer volume excluding the core particle volume ( For example, 99 5 vol% of the liquid phase, for example, 70 vol%, further up to a volume of 45 〇/〇 in terms of the layer volume excluding the core particle volume. In some embodiments, the sintering temperature can range from 600»c to about 8 〇〇 (rc). In a particular embodiment, the sintering temperature can range from 6 〇〇〇c to 1700 °C. For example, 1250. (: to 1700. (In another embodiment, the sintering temperature may range from 1700 ° C to about 8000 ° C. In a non-limiting embodiment, the sintering temperature may be 6 〇〇 to 1 700 ° C, and in the layer volume excluding the volume of the core particles, the amount of liquid phase 102496.doc 1362304 can be in the range of 6 to 44% by volume. Absolute pressure of a certain pressure, such as 'in the range of 0 absolute pressure to atmospheric pressure. "vacuum" sintering pressure is typically in the 丨-760 Torr (Ding 〇 (76 〇 =1 = 1 atmosphere), ... The handle is pressureless. Sintering. In this case, subatmospheric pressure is used. There are two purposes: to control the chemical reaction rate and control the physical process during different temperature ranges used during the sintering process. Not limited to) nitrogen, nitrogen, helium, hydrogen, helium, helium, helium , acetylene acetylene oxidation, carbon dioxide and their mixtures and related compounds. It should be understood that π no pressure " sintering only refers to sintering or consolidation at the sintering temperature, not during cold or warm pressing process (eg, cold Isobaric extrusion (cip) forms a pre-fired (or raw) article. During the compacting step, the external consolidation pressure is generally applied in an amount sufficient to form a "raw" object. It is clear to the skilled person that sintering Not carried out during warming or cooling. The bonding agents commonly used to increase the strength of the articles formed from the TCHP described herein include, but are not limited to, rocky soil, stearic acid, and ethyl bis-stearylamine ( EBS), plasticizers (such as 'polyethylene, polyethylene glycol or synthetic resin) and similar related organic compounds. Some TCHP core powders, such as nitrides, including but not limited to TiN, ZrN and HfN ' Reacting from the nitrogen to a high sintering temperature. Release of the Τι atom without a may consume the carbon WC coating, resulting in a de-stoichiometric condition that is detrimental to the mechanical properties of TCHP. It can be inhibited or promoted by using sub-atmospheric pressure. Examples of P reactions include oxidation and reduction reactions (eg, decarburization, deoxygenation, denitrification, degassing or chemical decomposition of different components of the core powder or coating in I02496.doc -20-1362304). Consistent sintered parts and further A dense and stable process is required to control these oxidation and reduction reactions. Some TCHP core particles are very irregular in shape and may require the addition of a lubricant to help them consolidate because they are not rounded by dissolution. In addition, thin 〇 and Co TCHP The coating needs to protect against oxygen and moisture that is not exposed to air, which may require additional polymeric protective coatings. Examples of physical TCHP methods that can be controlled by using subatmospheric pressure control include polymeric material delivery (e.g., debinding or delubing rate), rate of volatilization, rate of thermal transfer, and possible thermal decomposition of the constituent materials. Polymeric materials are used as dispersible cements and lubricants in such TCHP applications for protective encapsulation and increased shelf life, for example, including the foregoing, for example, paraffin, stearic acid, ethyl bis-stearylamine (EBS), plasticizers (such as polyvinyl alcohol, polyethylene glycol or synthetic resins) and similar related organic compounds. Pressures below atmospheric pressure are generally not used for consolidation purposes. The purpose of the absolute pressure above atmospheric pressure is to consolidate the PM parts. However, gas pressures above atmospheric pressure also solve the control problems of the above chemical reactions. It will be appreciated that the volume of the liquid phase in the outer or interlaminar layer may be increased by at least one parameter selected from the group consisting of sintering temperature, sintering pressure and binder material content. One non-limiting example of a cement material is cobalt. In the local = the whole TCHP body, the very uniform c〇 distribution reduces the high external pressure by allowing the sintering temperature to force to the 1275 C eutectic point to obtain the liquid phase i required for material transport and TCHp densification. need. I02496.doc 1362304 In sintered TCHP, even at the hypoeutectic temperature, the wet turbid angle of the recorded layer on the coating can be small and further, for example, can be ruthenium. In a specific embodiment, 'directly applied to the TCHP on the WC layer (4) only need to move a very short distance, ie wet turbidity and cover the WC coating. Between heating TCHI^, the outer atoms in each wc layer first diffuse, then Dissolved into the outer Co layer. The wc layer dissolves evenly from the outside to the inside. At TCHPt, these layers reach a thermodynamic equilibrium and have a liquid phase that is required to greatly reduce junction mobility. In some embodiments, the cobalt does not penetrate into the coating of the core particles. For example, there may be highly adjacent WCow coated surface coating structures that are typically close to the CVD coating on tool inserts and other articles. The CVD deposition of WC(i_x) polycrystals in a sedimentation degree can be as small as the conventionally ground wc·Co particles and more closely packed up to two orders of magnitude. During the wc(lx) coating carbonization to stoichiometry, the coating There is grain growth in the polycrystal (depending on the carbonization temperature). However, the close proximity of cobalt to these polycrystals should allow the coating polycrystal to dissolve uniformly around the WC coating, and equilibrium can limit grain growth. In 3 and 4, it can be seen that in the sintered wc coating structure, the polycrystals can be one order of magnitude smaller than the conventionally ground WC-Co polycrystals. In another embodiment, 'significant Co-combination occurs. Grain growth up to about 1 micron can occur in the region. The impermeability of the TCHP WC coating to Co intrusion of silver can be attributed, at least in part, to the following explanation. It goes without saying that WC and Co in TCHP are chemically similar to conventional ones. The WC and Co in the hard metal blend can be determined by evaluating the WC-Co phase diagram (see Figure 5) (see Figure 6), using a coating of 94% by weight (: -6 wt% c〇) The composition was sintered at 1500 ° C from 50% by volume of particles (75% by weight) WC coating 102496.doc -22· 1362304 When forming a typical TCHP target matrix, 87.1% by weight of the WC coating (or 92.7% of the initial 50% by volume WC coating) remains as a protective solid wc in the TCHP coating on the TCHP core particles. Externally dissolved, the residual solid WC can only be present as a target core-protective and structural coating. Due to the softening and near liquid phase, some particle rearrangements are expected, but only rearrangement is not sufficient to provide complete density'. Additional WC liquefaction. Even with very low liquid volume, a dense effect can be obtained. Since the liquid phase is uniformly distributed in the TCHP, it is almost completely along all wc surfaces without a combination or ladder. Very low volume liquid Co cement. Most liquid phase sintering can be provided. The WC dissolution should provide the rest of the liquid phase sintering. As mentioned above, the TCHP particles (the coating is generally dissolved from the outside, leaving undissolved protective properties around the core particles). The structural layer is re-sinked and nucleated to reinforce the existing particle coating, or as a power transmission pore and gap filler. In this paper, "gap filler refers to a material that fills the gap between adjacent particles (small space). The WC coating in the Co bond is only partially soluble for densification, wc reprecipitation repair/recrystallization and the integrity of the adjacent TCHP microstructure matrix. Only the Co and WC mobility required is the transport material to fill the coated The reduction between the core particles is required to be adjacent to the gap. On the Lina, there are at least two ways to increase the dissolution of the solute in the solvent: (曰1) increase the amount of solvent present (in a particular embodiment, c〇; WC4 ratio) '(2) increase the temperature of the solvent and solute' and (3) reduce the waste force on the solvent and solute. In fact, only two ways increase the amount of liquid phase existing between the sintered TCHP. Discuss the first two approaches. Some number of core particles (e.g., transition metal carbides and nitrides) will chemically interact with I02496.doc • 23-1362304 == cement. These core particles are called households: two! Increasing the temperature increase, even if the _sintering temperature: is increased enough to provide the amount required for the liquid phase used in the LPS, the thickness wc will still exist to protect the "soluble core" group of particles from unrecorded. Any additional liquid phase should be increased to a high temperature to achieve the desired minimum density to achieve full density ("lubricant + gap filler + capillary attracting material, for example, in a particular embodiment, such as a 1 micron core TCHP, TiN particles and WC^〇TlN volume 〇/〇 are equal, the initial WC coating (spherical model) will be almost 129 mm thick and will include about 5% by weight of the total particles. Dissolution at 1500 °C will only remove 79 Nano, or about 6% coating thickness, leaving about 121 nm, or about 94% initial coating thickness for core particle protection, inter-core particle distance uniformity and structural toughness. Due to the TCHP characteristics, The amount of binder phase solvent present, for example, by increasing the thickness of the cobalt layer, is another feasible sintering method that can be used according to the methods described herein. For example, increasing the weight percent of cobalt above the slippery "normal percentage in sintering as provided The methods required for dissolution, capillary action, WC kinetics, and TCHP densification become feasible. It should be remembered that in TCHp, WC is mainly present as a tough matrix material due to the true wear resistance of the positive core particles. The added cobalt will be added to the amount of liquid phase during sintering while increasing the fracture toughness after cooling. Sintering can occur in a process selected from the group consisting of sintering extrusion, vacuum, powder injection molding, plasticizing extrusion. , hot pressing, hot isostatic pressing (HIP), sintering-HIP, sintering furnace, laser cladding method, plasma cladding, high-speed oxygenated fuel 102496.doc •24· 1362304 (HVOF), spark plasma sintering , pressure plasma sintering, pressure transfer media, dynamic / explosive compaction, sintering casting, rapid prototyping, electron beam and arc. In TCHP, WC coating protects the core particles. First, during sintering, especially In the "soluble cores" group, the WC coating protects the core coating from dissolution by the metal binder' and also protects the substrate from harmful contamination such as TiN, ZrN, NbC. High wear resistance TCHP during use The core particles protect the wC-Co branch matrix from wear after sintering, while the support matrix protects the fragile phase from breaking and pulling out. Figure 2 depicts the sintered microstructure of a typical TCHP material with small hard core particle size and in-crystal Thin cobalt linkage Separating less than 1 micron toughness, TCHp structure improvement of nano-sized shells, for example, elasticity, hardness, fracture toughness, and strength. In a non-limiting embodiment, even with low hardness materials (eg, cobalt), due to The imaginary stress near the surface (and close to the surface with submicron grains) self-dislocation, the composite property is still higher than that in the wear composite.,,,,,,,,,,,,,,,,,,,,, (e.g., toughness, strength coefficient of friction, and hardness) balance. In a non-limiting embodiment, > and other tools manufactured from TCHP have been observed to improve the operation, such as the lower interface between the workpiece and the tool. Friction coefficient, resulting in reduced burnout and formation of craters, and requires less 4 force and _ use of external agent, resulting in longer tool life and better process control; (8) reaction with iron 4, reducing the subsequent and diffusion, The side or the mold is worn, and the life of the die is delayed; and (4) the microstructure of the sintered tool, wherein the particles j 102496.doc -25-1362304 strong money material (for example, wc) is formed for the sanitary ware many The pore-supporting structure, (iv), provides a protective layer for the hard particle core (for example, the surface is compliant and tightly bonded, keeping them in place and allowing optimal exposure and hard phase on the surface of the anti-wear tool Keep the manufactured objects in contrast, in the conventional method...:

Drastically reduced in the strength of the joint present between the particles, and the bonding agent itself reduces the level of boring and f-boom & or wherein the sintered article is completely coated to impart hardness 'where the thin coating has a limited life or break . Arranging the hard phase alloy as the core particles on the inside rather than on the outside makes the hard phase alloy (exposed to the outer surface after completion of the grinding) more likely to distribute in a larger proportion or thickness throughout the sintered microstructure than in any known materials. . This can, for example, increase wear resistance, reduce chemical interaction with the workpiece, and significantly reduce friction system h tool life can be improved by finely refining the surface grains that are worn or pulled by the opposite sliding surface. The wear resistance and adhesion f of many possible core materials are also known from their 11 quality in the known materials, so that their properties as core particles can be pre-shaved in certain non-limiting embodiments in accordance with the present invention. Since the particles are coated with known materials (e.g., wc), blending and sintering the ruthenium coated particles having several different core materials will promote improved performance. This reduces development and testing costs while providing the final material with unique properties. Therefore, the sintered microstructure is designed to have high strength, high modulus of elasticity, and fracture toughness when each particle has a tough shell (intermediate layer) capable of strongly adhering its adjacent particles to form a toughness support system throughout the sintered article substrate. And sintered materials with a combination of hard alloy content. 102496.doc -26· 1362304 In some embodiments, the macroscopic structure of the resulting article is a porous microstructure consisting of bovine, = tight, inter-bonded coated particle shells, and at least one species A material selected from the group consisting of mechanically and chemically bonded core particles, crystals, fibers and whiskers, and which is exposed to the cross-section of the outer surface during the grinding and polishing process to optimize the combination of the different materials used for the core particles and the surrounding intermediate layer. Combine the properties of normal objects, such as strength and hardness, at (4) the level at which the material is unattainable. This concept can be given to the material designer to individually or in combination: a plurality of tools and provide for the TCHP particle structure (intermediate layer thickness, size, core material) and mixture (to integrate different powders into tools and object areas) to accommodate An easy way for an object or tool to meet the many easy, and overall controls of many different unique, combined, and specialized needs. In addition, the use of standard strong materials (such as 'wc) as a representative external particle shell dramatically reduces research, development and industrialization work, because only one substance is used to react the precursor gas (for example, tungsten carbide) to coat the powder particles instead of multiple Many complex precursors and reactant gases used in external substrate coatings. These particulate materials appear to be sintered as if they are made of tungsten carbide particles, for example, it is known that a bonding agent (e.g., cobalt) is strongly bonded to adjacent tungsten carbide particles. For example, the thickness of the tungsten carbide coating on the particles can be increased to meet more challenging strength applications or reduced in more critical wear applications to solve most design problems. For example, it is easy to increase the core particle size to meet the more stringent requirements for anti-wearing shells or to reduce for more southern strength applications. By selecting the core material, it is also possible to achieve different properties (such as hardness and friction system I02496.doc -27-1362304) which are known or found to perform better in specific applications for side wear or crater wear. Different core particle materials. The above thickness, diameter and core powder parameters can also be blended to solve most standard application problems. The article made of TCHP particles makes the combination of the strength, hardness, high modulus of elasticity, fracture toughness, low action with the workpiece and low mechanical friction of the known material in the material that does not match the combined nature. . CHP has an unlimited use in manufacturing, surface modification or component, assembly and mechanical repair. The single component group includes cutting, forming, grinding, and oil and mining and construction tools. Non-tool components include biopharmaceutical, military, electronics, sports, heat treatment, and cosmetic applications. A wide range of industries ~ found in agriculture, civil, logging and paper, petrochemical, rubber and plastic, transportation, aircraft / aerospace, marine 'building and energy sector. Therefore, the material is extremely suitable for a wide range of objects, including, for example: tools such as wire drawing dies, extrusion dies, forging dies, cutting and stamping dies, models, forming rolls, injection molding, shearing, drilling, milling and lathes. Tools, saws, hobs, irons, reamers, faucets and moulds; individual mechanical parts such as gears, cams, journals, nozzles, seals, valve seats, pump impellers, winches, sheaves, bearings and wear surfaces; Integrating and co-sintering 7C parts to replace the internal combustion engine connecting rods, bearings, and/or providing hard surface areas in powdered metal (P/Μ) mechanical parts to replace the forged or machined steel parts using heat treated areas, Such as camshafts, transmission parts, printer/photocopyer parts; heavy industrial items such as deep wells, teeth used in mining and earthmoving equipment, hot rolls used in rolling mills; and electromechanical components such as storage drive read heads Special magnets. I02496.doc -28- Macroscopic sentences rather than externally coated consolidated TCHP objects can give or suppliers the opportunity to economically re-grind and reuse the initial abrasive objects: Tools such as wire drawing dies, augers, sharp knives and water nozzles are especially important. Those skilled in the art should understand that changes may be made without departing from the scope of the invention. Therefore, the present invention is not limited to the specific embodiments disclosed, but is intended to cover various modifications within the spirit and scope of the invention as defined by the appended claims. Unless otherwise stated, all numbers indicating the amount of ingredients, reaction conditions, etc. used in the specification and claims are in all cases t should be treated as "about" 5%. Therefore, unless the opposite is the case, the S-characteristics in the S-book and the extravagant terms are approximate values that can be changed by seeking the desired properties of the present invention. Figure 1 is a pseudo binary WC-Co phase diagram. Figure 2 represents a typical TCHP sintered object. Figure 3 is a SEM photograph showing that the TCHP structure is still intact even when too much Co is contained. Figure 4 shows an SEM photo 'shown in Effective prevention of wc layer dissolution during and after sintering Figure 5 represents a model of TCHp material at different sintering temperatures. This compares particle dissolution under different liquid phase sintering conditions. Figure 6 shows the calculation of wC-Co solids at different temperatures and cobalt content. Table of liquid phase compositions. Figure 7 is a photomicrograph of a liquid phase sintered TCHP.

Claims (1)

1362304 X. Patent application scope: 1. Method for forming an object No. 094119344 Patent Application Order Replacing the scope of the patent application (December 100) [0° year to month V曰修(<) Original method This method includes * _ ' --- 1 provides a plurality of core particles consisting of a core particle material or a plurality of different core particle materials selected from the group consisting of metal and metalloid nitrides, metal and metalloid carbides, metals and a group of metalloid carbonitrides, metal and metalloid borides, metal and metalloid oxides, metal and metalloid sulfides, metal and metalloid tellurides, and diamonds; 1% to 8% of atoms provide an intermediate layer on the surface of the core particle on a majority of the core particles, the intermediate layer comprising a first compound having a composition different from that of the core particle material and having a relatively high fracture toughness The second compound is capable of interfacing with the core particulate material and is selected from the group consisting of iron, cobalt, nickel, copper, titanium, aluminum, magnesium, lithium lanthanum, gold, gold, and mixtures thereof. a metal bond of the group ' thereby forming a coated particle; applying an outer layer to the coated particle on the outer surface of the intermediate layer by depositing atoms, wherein the atom comprises a layer selected from the group consisting of iron, cobalt, nickel, and mixtures thereof a group of metals 'to form a substantially continuous outer layer on the intermediate layer, thereby forming component particles; forming a plurality of the component particles into an article; at a temperature sufficient to liquefy at least a portion of the outer layer and sufficient from the outer layer Forming a liquid in which the intermediate layer dissolves the article to provide a substantial amount of liquid to sinter the article to a substantially complete density, from 600 ° C to 1700 ° C, and comprising the outer layer, wherein the intermediate layer of the sintering temperature or The amount of the liquid phase of the two 102496-100J214.doc 1362304 is in the range of 6 to 44% by volume based on the volume of the component particles, which does not include the volume of the core particle and the portion of the intermediate layer in which the sintering remains. Undissolved; and solidifying the liquid formed from the outer layer and the intermediate layer, whereby the atoms deposited to form the intermediate layer are reprecipitated to the undissolved in the intermediate layer The duties of the matrix, wherein the matrix comprises the intermediate compound of discrete crystals in the adhesive of the outer layer, the fluid system which is formed of from the outer layer and the intermediate layer in the liquid before the chemical core particle of interacting curing. 2. The method of claim 1, wherein the core particulate material has the chemical formula MaXb, wherein the germanium is selected from the group consisting of titanium, zirconium, hafnium, hunger, sharp, group, chromium, key, crane, methane, copper, copper and strontium. a group of metals; X is an element selected from the group consisting of atmosphere, carbon, rotten, sulfur, and oxygen; a and b are greater than 〇 and include 14 numbers. 3. The method of claim 1, wherein the core particulate material is selected from the group consisting of dn, TiCN, TiC, TiB2, ZrC, ZrN, ZrB2, HfC, HfN, HfB2, TaB2, VC, VN, eBN, hBN, A1203, Si3N4 , SiB6, SiAlCB, B4C, B203, W2B5, WB2, WS2, AIN, AlMgB丨4 'MoS2, MoSi2, Mo2B5, MoB2 and a mixture thereof. 4. A method of forming an article, the method comprising: providing a plurality of core particles consisting of a core particle material or a plurality of different core particle materials selected from the group consisting of: TiCN, TiC, TiB2, ZrC, ZrN , ZrB2, HfC, HfN, 102496-1001214.doc 1362304 HfB2, TaB2, VC, VN, cBN, hBN 'Al2〇3, Si3N4, SiB6, SiAlCB, B4C, B203, W2B5, WB2, WS2, AIN, AlMgB14, M0S2 a group of MoSi, M〇2B5, MoB2, and diamond; by depositing atoms on the surface of the core particle, providing a majority of the core particles in an amount ranging from 10% by weight to 80% by weight based on the weight of the article An intermediate layer comprising a second compound having a composition different from the core particle material and having a relatively high fracture toughness, the second compound being selected from the group consisting of WC, TaC, W2C, and a mixture of WC and W2C Grouping, thereby forming coated particles; adding an outer layer to the coated particles by depositing a metal atom selected from the group consisting of iron, inscription, recording, and mixtures thereof, in On the middle layer Forming a continuous continuous outer layer, thereby forming component particles; forming a plurality of component particles into the article; at a temperature sufficient to liquefy at least a portion of the outer layer and sufficient to dissolve 5 to 90% by volume in the liquid formed from the outer layer The layer sinters the article at a time to provide an effective amount of liquid to achieve a substantially complete density, the solid portion of the intermediate layer preventing chemical interaction of the liquid with the core particle, wherein the sintering causes a portion of the intermediate layer to be undissolved; Curing a liquid formed from the outer layer and the intermediate layer, whereby the atoms deposited to form the interbing layer are reprecipitated into a matrix outside the undissolved portion of the interbing layer, wherein the base f comprises The discrete crystals of the intermediate compound are crystallized in the binder of the outer layer, wherein the liquid system formed from the outer layer and the intermediate layer is solidified by a chemical interaction between the liquid and the core particle 102496-1001214.doc 1362304. 5. The method of claim 1, 2 or 3, wherein the sintering temperature and time are not, resulting in complete dissolution of the intermediate layer. A method of claim 1, 2 or 3, wherein the sintering temperature and time cause $50% of the intermediate layer to dissolve. The method of claim 1, 2 or 3, wherein the sintering temperature and time conductance are 50-99% of the intermediate layer dissolved. 8’. The method of claim 1, 2 or 3 wherein the solid portion of the intermediate layer terminates the chemical interaction of the liquid with the core particles. The method of claim 1, 2 or 3, wherein the material consists of a group consisting of wc w2c, tool steel, dolothyridine, and tantalum carbide. 1 〇. If you ask gray IS 1, 〇 I. 102496-1001214.doc 其中 'where the intermediate layer comprises a pigment selected from the group consisting of a gloss and a delustered nano steel alloy, wherein the coated particles have a small size, wherein the coated particles have a small size, wherein the coated particles have Small wherein the coated particles have a small size, wherein the coated particles have a small size, wherein the coated particles have the method of claim 1, 2, 3 or 4, wherein the intermediate layer has a core after sintering The thickness of the particles ranges from 5 °/〇 to 50%. 17. 18. The method of claim 1, 2, 3 or 4, wherein the outer layer has a range of 3% to 12% of the coated particle diameter after sintering thickness. The method of claim 1, 2, 3 or 4, wherein the outer layer further comprises one or more layers selected from the group consisting of metals, ceramics, cements, sintering aids, and polymeric materials. The method of claim 1, 2, 3 or 4, wherein the intermediate layer is selected from at least one selected from the group consisting of chemical vapor deposition, physical vapor deposition, electro-deposition, laser dazzling or deposition, plasma cladding, magnetic Plasma deposition, electrochemical plating, electroless plating, sputtering, solid phase synthesis, solution chemical deposition methods, and combinations of such methods are deposited. The method of claim 1, 2, 3 or 4, wherein the outer layer is selected from at least one selected from the group consisting of chemical vapor deposition, physical vapor deposition, plasma deposition, laser deposition or deposition, plasma cladding, and magnetic power. Deposition by slurry deposition, electrochemical plating, electroless plating, sputtering, solid phase synthesis, and solution chemical deposition methods. The method of claim 1, 2, 3 or 4, wherein the intermediate layer is attached at a temperature of ι 25 ° (: to 180 〇. (: a range of temperatures. The method of claim 1, 2, 3 or 4, wherein The intermediate layer is deposited at a temperature in the range of 2 (rc to 12 5 C. The method of claim 1, 2, 3 or 4 wherein the intermediate layer is at a temperature ranging from 18 ° C to 80 ° t The method of claim 1, 2, 3 or 4, wherein the intermediate layer is deposited at a temperature in the range of 2〇〇102496-1001214.doc 1362304 C to 80〇. 25. as claimed in claim 1, 2 The method of 3, 4, wherein the outer layer is deposited at a temperature of 2 (Γ to: 125 ° C. 26. The method of claim 1, 2, 3 or 4, wherein the outer layer is at 125 27. The method of claim 1, 2, 3 or 4 wherein the outer layer is deposited at a temperature in the range of from 200 〇c to 550 ° C. 28. If the requirements i, 2 The method of 3, 4, wherein the sintering temperature is in the range of 6 ° C to 1275 ° C. 29 - a method of forming an article, the method comprising: providing a plurality of core particles Or a plurality of core particles composed of different core material selected from the group consisting of TiN, TiCN, TiC, TiB2, ZrC, ZrN, ZrB2, HfC, HfN, HfB2, TaB2, VC, VN, cBN, hBN, A1203 a group consisting of Si3N4 'SiB6, SiAlCB, B4C, B203, W2B5, WB2, WS2, AIN, AlMgB14, MoS2, MoSi2, Mo2B5, MoB2, and diamond; by deposition, the weight ranges from 1% to 8 〇% of the atoms provide an intermediate layer on the surface of the core particle on a majority of the core particles, the intermediate layer comprising a second compound having a composition that is different from the core particle material and having a relatively high fracture toughness, the second compound Selected from the group consisting of wc, TaC, WzC, and a mixture of WC and we, thereby forming coated particles; the atoms of the deposited metal form a substantially continuous outer layer on the intermediate layer, 102496-1001214.doc 1362304 Applying an outer layer to the coated particles, thereby forming component particles, wherein the metal is selected from the group consisting of iron, cobalt, nickel, and mixtures thereof; forming a plurality of the particles of the component to form an article; The outer layer is liquefied at a temperature sufficient to dissolve the article from 5 to 90% by volume of the inter-t layer in the liquid formed from the outer layer to provide an effective primary liquid to achieve a substantial full density wherein the sintering temperature is self-enthalpy 700. (: to 8 〇〇 (rc, and wherein the sintering retains a portion of the intermediate layer undissolved; and solidifies the liquid formed from the outer layer and the intermediate layer, thereby depositing to form the intermediate layer Recrystallizing the atom into a matrix outside the undissolved portion of the intermediate layer, wherein the matrix comprises discrete crystals of the intermediate compound in the binder of the outer layer, wherein the liquid system formed from the outer layer and the intermediate layer Curing before the chemical interaction of the liquid with the core particles. 30. The method of claim i, 2, 3 or 4, wherein the outer layer comprises a weight of 5% of the weight of the object. /〇 to an amount in the range of 3 wt%. The method of claim 2, 3 or 4, wherein the outer layer comprises from 3% by weight to 18% by weight of the article. /. The amount of scope. 3 2. As requested! The method of 2, 3 or 4 wherein the outer layer comprises an amount in the range of from 18 weight percent to about 45 weight percent based on the weight of the article. 3. The method of claim 2, wherein the intermediate layer comprises 60 weight ❶/ by weight of the object. A material selected from the group consisting of WC, TaC, W2C, WC, and W2C in an amount ranging from 98% by weight. 3 4. If you are asking for it! The method of 2, 3, wherein the intermediate layer comprises an amount selected from the group consisting of WC, TaC, W2c, WC, and w2c in an amount ranging from 10% by weight to 6% by weight based on the weight of the object 102496-1(8) 1214.doc 1362304 Material. 35. The method of claim 1, wherein the intermediate layer comprises an amount selected from the group consisting of Wc, TaC, w2c, WC, and W2C in an amount ranging from 5% by weight to 1% by weight based on the weight of the article. material. 36. The method of claim 1, 2, 3 or 4, wherein the sintering consolidation occurs primarily from capillary forces. 37. A method of π, ???, 2, 3 or 4, wherein the volume of the liquid phase is increased by increasing a parameter selected from the group consisting of sintering temperature and cobalt content. 3 8. If the month is long! The method of 2, 3 or 4, wherein the consolidation is selected from the group consisting of nitrogen, I, helium, hydrogen, helium, neon, xenon, methane, acetylene oxide, carbon dioxide, mixtures thereof and compounds 39. The method of claim 37, wherein the process gas system is provided in the range of absolute pressure to atmospheric pressure. Further comprising the method of claim 40. The method of claim 1, 2, 3 or 4, wherein the β 4 4 is at least one selected from the group consisting of stone bad, stearic acid, ethyl stearyl amide (EBS), The additives of polyvinyl alcohol and polyethylene glycol are mixed with a plurality of particles of this component. 41. The method of claim 1, 2, 3 or 4, 1275 C to 170 〇. Within the scope of 〇. Wherein the sintering temperature is in the range of 42. The method of claim 1 is the method of claim 1. The method of claim 1 wherein the sintering temperature is greater than 1315. (: wherein the sintering temperature is greater than 1400 ° C. wherein the sintering temperature is greater than 1500 ° C. 102496-I001214.doc